JP2018095768A - Surface-treated semiconductor nano crystal and color filter using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a surface-treated semiconductor nano crystal having excellent dispersion stability in various organic solvents and resin materials, a resin composition containing the nano crystal, a color filter, and a display.SOLUTION: The surface-treated semiconductor nano crystal contains a semiconductor nano crystal (A) and a calixarene compound (B) represented by formula (1) as the essential components (Ris an aliphatic hydrocarbon group; Ris a polar group or the like; Ris H, an aliphatic hydrocarbon group or an aryl group; n is an integer of 2-10; and * represents a binding site with an aromatic ring).SELECTED DRAWING: None

Description

  The present invention relates to a surface-modified semiconductor nanocrystal, a resin composition containing the surface-modified semiconductor nanocrystal, a color filter, and a display.

  Semiconductor nanocrystals are phosphors called quantum dots, QDs, nanocrystals, etc., and are characterized by high luminous efficiency. In order to use semiconductor nanocrystals more easily and with good handling, a technique for dispersing the semiconductor nanocrystals in an organic solvent, a resin material, water, or the like has been studied (see Patent Document 1). However, the currently known methods have problems such as insufficient dispersion stability and limitation of usable organic solvents.

Special table 2002-510866 public information

  Therefore, the problem to be solved by the present invention is a surface-modified semiconductor nanocrystal with excellent dispersion stability in various organic solvents and resin materials, a resin composition containing the surface-modified semiconductor nanocrystal, a color filter, and a display It is to provide that.

  As a result of intensive studies to solve the above problems, the present inventors have found that various surface-modified semiconductor nanocrystals obtained using a calixarene compound having a specific chemical structure as a dispersant for semiconductor nanocrystals have various properties. It has been found that the dispersion stability in various organic solvents and resin materials is excellent, and the present invention has been completed.

  That is, the present invention relates to a semiconductor nanocrystal (A) and the following structural formula (1)

（式中Ｒ^１はエーテル結合部位、カルボニル基、水酸基の何れかを有していてもよい脂肪族炭化水素基である。Ｒ^２は極性基、又は極性基を有する構造部位である。Ｒ^３は水素原子、置換基を有していてもよい脂肪族炭化水素基、置換基を有していてもよいアリール基の何れかである。ｎは２〜１０の整数である。＊は芳香環との結合点である。）
で表される分子構造を有するカリックスアレーン化合物（Ｂ）とを必須の構成成分とする被表面修飾半導体ナノ結晶に関する。

(Wherein R ¹ is an aliphatic hydrocarbon group which may have any of an ether bond site, a carbonyl group and a hydroxyl group. R ² is a polar group or a structural site having a polar group. R ³ Is a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, or an aryl group which may have a substituent, n is an integer of 2 to 10. * is an aromatic ring Is the point of attachment to.)
It is related with the surface modified semiconductor nanocrystal which uses the calixarene compound (B) which has the molecular structure represented by these as an essential component.

  The present invention further relates to a resin composition containing the surface-modified semiconductor nanocrystal.

  The present invention further relates to a color filter using the surface-modified semiconductor nanocrystal.

  The present invention further relates to a display using the color filter.

  According to the present invention, there are provided a surface-modified semiconductor nanocrystal with excellent dispersion stability in various organic solvents, a resin composition containing the surface-modified semiconductor nanocrystal, a color filter, and a display. Can do.

Hereinafter, the present invention will be described in detail.
The surface-modified semiconductor nanocrystal of the present invention comprises a semiconductor nanocrystal (A) and the following structural formula (1)

（式中Ｒ^１はエーテル結合部位、カルボニル基、水酸基の何れかを有していてもよい脂肪族炭化水素基である。Ｒ^２は極性基、又は極性基を有する構造部位である。Ｒ^３は水素原子、置換基を有していてもよい脂肪族炭化水素基、置換基を有していてもよいアリール基の何れかである。ｎは２〜１０の整数である。＊は芳香環との結合点である。）
で表される分子構造を有するカリックスアレーン化合物（Ｂ）とを必須の構成成分とする。

(Wherein R ¹ is an aliphatic hydrocarbon group which may have any of an ether bond site, a carbonyl group and a hydroxyl group. R ² is a polar group or a structural site having a polar group. R ³ Is a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, or an aryl group which may have a substituent, n is an integer of 2 to 10. * is an aromatic ring Is the point of attachment to.)
And a calixarene compound (B) having a molecular structure represented by the formula:

  The semiconductor nanocrystal (A) will be described. As used herein, the term “nanocrystal” preferably refers to a particle having at least one length of 100 nm or less. The shape of the nanocrystal may have any geometric shape and may be symmetric or asymmetric. Specific examples of the shape of the nanocrystal include an elongated shape, a rod shape, a circle shape (spherical shape), an ellipse shape, a pyramid shape, a disc shape, a branch shape, a net shape, and an arbitrary irregular shape.

  As an example of the semiconductor nanocrystal (A), one having a core containing the semiconductor compound (1) and a shell containing the semiconductor compound (2) can be given. The shell covers at least a part of the core. Each of the semiconductor compound (1) and the semiconductor compound (2) may be composed of one type of semiconductor compound or a plurality of types of semiconductor compounds. Further, the semiconductor compound (1) and the semiconductor compound (2) may be the same or different. The shell may be composed of a plurality of layers. That is, in addition to the shell containing the semiconductor compound (2), one or more shells containing the semiconductor compound (n) may be provided. When the shell is composed of a plurality of layers, the semiconductor compounds contained in each shell may be the same as or different from each other.

Examples of the preferred form of the semiconductor nanocrystal (A) include the following three patterns. 1. A form having a core containing a semiconductor compound (1) and a shell containing a semiconductor compound (2), wherein the semiconductor compound (1) and the semiconductor compound (2) are the same. 2. A form having a core containing a semiconductor compound (1) and a shell containing a semiconductor compound (2), wherein the semiconductor compound (1) and the semiconductor compound (2) are different. A core including a semiconductor compound (1), a shell including a semiconductor compound (2), and a shell including a semiconductor compound (3), wherein the semiconductor compound (1) and the semiconductor compound (2) are different from each other. And the semiconductor compound (2) and the semiconductor compound (3) are different from each other

  Examples of the semiconductor compounds (1), (2), and (n) include II-V group semiconductor compounds, II-VI group semiconductor compounds, III-IV group semiconductor compounds, III-V group semiconductor compounds, and III-VI groups. Semiconductor compound, IV-VI group semiconductor compound, I-III-VI group semiconductor compound, II-IV-VI group semiconductor compound, II-IV-V group semiconductor compound, I-II-IV-VI group semiconductor compound, Group IV Examples thereof include an element or a compound containing the element. These may be used alone or in combination of two or more.

Examples of the II-V group semiconductor compound include Zn ₃ N ₂ , Zn ₃ P ₂ , Zn ₃ As ₂ , Cd ₃ N ₂ , Cd ₃ P ₂ , and Cd ₃ As ₂ . The II-VI group semiconductor compounds include, for example, binary compounds such as ZnO, ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, HgS, HgSe, HgTe; ZnSeS, ZnSeTe, ZnSTe, CdZnSe, CdZnSe, CdZnTe, CdSeS, CdSeTe, CdSTe, CdHgS, CdHgSe, CdHgTe, HgSeS, HgSeTe, HgSTe, HgZnS, HgZnSe, ternary compounds such as HgZnTe; CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, CdHgZnTe, HgZnSeS, HgZnSeTe, such HgZnSTe four yuan Compounds and the like. Examples of the group III-IV semiconductor compound include B ₄ C ₃ , Al ₄ C ₃ , and Ga ₄ C ₃ . The III-V semiconductor compound includes, for example, binary compounds such as BP, BN, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb; Ternary compounds such as GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP; GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInPAsInGas And quaternary compounds such as InAlNAs, InAlNSb, InAlPAs, and InAlPSb. Examples of the group III-VI semiconductor compound include Al ₂ S ₃ , Al ₂ Se ₃ , Al ₂ Te ₃ , Ga ₂ S ₃ , Ga ₂ Se ₃ , Ga ₂ Te ₃ , GaTe, In ₂ S ₃ and In _2. Examples include Se ₃ , In ₂ Te ₃ , InTe, and the like. Examples of the IV-VI group semiconductor compound include binary compounds such as SnS, SnSe, SnTe, PbS, PbSe, PbTe; SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbSe, SnPbSe, SnPbSe, SnPbSe, SnPbSe Quaternary compounds such as SnPbSSe, SnPbSeTe, and SnPbSTe; Examples of the I-III-VI group semiconductor compound include CuInS ₂ , CuInSe ₂ , CuInTe ₂ , CuGaS ₂ , CuGaSe ₂ , CuGaSe ₂ , AgInS ₂ , AgInSe ₂ , AgInTe ₂ , AgGaSe ₂ , AgGaTe ₂ , and AgGaTe _2. Can be mentioned. Examples of the group IV element or the compound containing the element include C, Si, Ge, SiC, and SiGe. Among them, CdS, CdSe, CdTe, ZnS , ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, GaP, GaAs, GaSb, InP, InAs, InSb, CuInS 2, CuInSe 2, CuInTe 2, CuGaS 2, CuGaSe 2, CuGaTe ₂ , AgInS ₂ , AgInSe ₂ , AgInTe ₂ , AgGaS ₂ , AgGaSe ₂ , AgGaTe ₂ , Si, C, and Ge are preferably one or more.

  The emission color of the semiconductor nanocrystal (A) is not particularly limited, and may be any color such as a semiconductor nanocrystal for red light emission, a semiconductor nanocrystal for green light emission, and a semiconductor nanocrystal for blue light emission. In general, the emission color of a semiconductor nanocrystal depends on the particle size according to the solution of the Schrodinger wave equation of the well-type potential model, but also depends on the energy gap of the semiconductor nanocrystal. The light emission color is selected by adjusting.

  The upper limit of the wavelength peak of the fluorescence spectrum of the red semiconductor nanocrystal is 665 nm, 663 nm, 660 nm, 658 nm, 655 nm, 653 nm, 651 nm, 650 nm, 647 nm, 645 nm, 643 nm, 640 nm, 637 nm, 635 nm, 632 nm or 630 nm. Preferably, the lower limit of the wavelength peak is preferably 628 nm, 625 nm, 623 nm, 620 nm, 615 nm, 610 nm, 607 nm or 605 nm.

  The upper limit of the wavelength peak of the fluorescence spectrum of the green semiconductor nanocrystal is preferably 560 nm, 557 nm, 555 nm, 550 nm, 547 nm, 545 nm, 543 nm, 540 nm, 537 nm, 535 nm, 532 nm or 530 nm, and the lower limit of the wavelength peak is It is preferably 528 nm, 525 nm, 523 nm, 520 nm, 515 nm, 510 nm, 507 nm, 505 nm, 503 nm or 500 nm.

  The upper limit of the wavelength peak of the fluorescence spectrum of the blue semiconductor nanocrystal is preferably 480 nm, 477 nm, 475 nm, 470 nm, 465 nm, 463 nm, 463 nm, 460 nm, 457 nm, 455 nm, 452 nm or 450 nm, and the lower limit of the wavelength peak is , 450 nm, 445 nm, 440 nm, 435 nm, 430 nm, 428 nm, 425 nm, 422 nm or 420 nm.

  It is desirable that the semiconductor material used for the red semiconductor nanocrystal has a peak wavelength of light emission in the range of 635 nm ± 30 nm. Similarly, it is desirable that the semiconductor material used for the green semiconductor nanocrystal has an emission peak wavelength in the range of 530 nm ± 30 nm. The semiconductor material used for the blue semiconductor nanocrystal preferably has an emission peak wavelength in the range of 450 nm ± 30 nm.

  Examples of the semiconductor material constituting the semiconductor nanocrystal (A) include the following for each emission color. Red: CdSe semiconductor nanocrystals, CdSe rod-shaped semiconductor nanocrystals, rod-shaped semiconductor nanocrystals having a core-shell structure in which the core contains CdSe and the shell contains CdS, and the core-shell structure in which the core contains ZnSe and the shell contains CdS A rod-shaped semiconductor nanocrystal with a core, a semiconductor nanocrystal with a core-shell structure with a core containing CdSe and a shell with CdS, a semiconductor nanocrystal with a core-shell structure with a core containing ZnSe and a shell containing CdS, CdSe and ZnS, Mixed crystal semiconductor nanocrystals, mixed crystal rod-shaped semiconductor nanocrystals of CdSe and ZnS, InP semiconductor nanocrystals, InP rod-shaped semiconductor nanocrystals, mixed crystal semiconductor nanocrystals of CdSe and CdS, CdSe and CdS mixed crystal rod-shaped semiconductor nanocrystal, ZnSe and CdS mixed crystal semiconductor Roh crystal, such as rod-shaped semiconductor nanocrystals of mixed crystal of ZnSe and CdS. Green: CdSe semiconductor nanocrystal, CdSe rod-shaped semiconductor nanocrystal, mixed crystal semiconductor nanocrystal of CdSe and ZnS, mixed crystal rod-shaped semiconductor nanocrystal of CdSe and ZnS, InP semiconductor nanocrystal, InP Rod-shaped semiconductor nanocrystals and so on. Blue: ZnSe semiconductor nanocrystal, ZnSe rod-shaped semiconductor nanocrystal, ZnS semiconductor nanocrystal, ZnS rod-shaped semiconductor nanocrystal, semiconductor nanocrystal having a core-shell structure in which the core contains ZnS and the shell contains ZnSe, the core A rod-shaped semiconductor nanocrystal having a core-shell structure in which ZnS and CdS are included and the shell is ZnSe.

  When the semiconductor nanocrystal (A) is a so-called quantum rod, the length (average length) in the major axis direction of the quantum rod is preferably 15 to 120 nm, preferably 20 to 80 nm, and preferably 25 to 70 nm. More preferred. The length (average length) in the minor axis direction of the quantum rod is preferably 1 to 11 nm, more preferably 2 to 8 nm, and further preferably 3 to 7 nm. Moreover, the shape of the said quantum rod should just be an elongate body extended in one specific direction, and a cylindrical shape, a polygonal column shape, a polygonal pyramid shape, a cone shape, etc. are mentioned. The aspect ratio of the quantum rod (average length in the major axis direction of the quantum rod / average length in the minor axis direction of the quantum rod) is preferably 3 to 30, more preferably 4 to 20, and more preferably 5 to 10 Is more preferable.

  The calixarene compound (B) is a component that functions as a surface modifier or dispersant for the semiconductor nanocrystal (A), and for the purpose of improving the dispersibility of the semiconductor nanocrystal (A) in an organic solvent, a resin component, or the like. Use. The calixarene compound (B) is used in a relatively small amount because the dispersibility of the semiconductor nanocrystal (A) is remarkably higher than that of a surface modifier or dispersant generally known so far. In addition, surface-modified semiconductor nanocrystals that are sufficiently excellent in dispersion stability in various organic solvents can be obtained. The semiconductor nanocrystal (A) and the calixarene compound (B) may be chemically bonded or may not be bonded.

In the structural formula (1), R ¹ is an aliphatic hydrocarbon group which may have any of an ether bond site, a carbonyl group and a hydroxyl group, and is an affinity group with a dispersion medium such as an organic solvent or a resin material. Is a structural site that functions as The aliphatic hydrocarbon group may be any of a straight chain type, a branched structure, an unsaturated bond, or a non-saturated structure, and the number of carbon atoms is not particularly limited. When the aliphatic hydrocarbon group has an unsaturated bond, the number thereof may be one or plural, and the position of the unsaturated bond in the aliphatic hydrocarbon group is not particularly limited. When R ¹ is an aliphatic hydrocarbon group having any of an ether bond site, a carbonyl group, and a hydroxyl group, the number of ether bond sites, the carbonyl group, the hydroxyl group, the substitution position, and the like are not particularly limited. Moreover, you may have 2 or more types of an ether bond part, a carbonyl group, and a hydroxyl group. When R ¹ has a plurality of ether bond sites, it may be a so-called polyoxyalkylene structure. When R ¹ has a hydroxyl group, it is preferable to have a hydroxyl group at the end of R ¹ . Especially, since the said semiconductor nanocrystal (A) can be disperse | distributed more stably with respect to various dispersion media, it is preferable that R1 is an aliphatic hydrocarbon group. The number of carbon atoms is preferably in the range of 1-18, more preferably in the range of 1-12, and particularly preferably in the range of 1-6.

N in the structural formula (1) is an integer of 2 to 10. Among them, those in which n is 4, 6 or 8 are preferable because they are structurally stable. In the structural formula (1), the bonding positions of R ¹ and R ² and the position of the bonding point represented by * are not particularly limited, and may have any structure. Especially, since it becomes the calixarene compound (B) which is further excellent in performance as a dispersant for the semiconductor nanocrystal (A), the following structural formula (1-1) or (1-2)

（式中Ｒ^１はエーテル結合部位、カルボニル基、水酸基の何れかを有していてもよい脂肪族炭化水素基である。Ｒ^２は極性基、又は極性基を有する構造部位である。Ｒ^３は水素原子、置換基を有していてもよい脂肪族炭化水素基、置換基を有していてもよいアリール基の何れかである。ｎは２〜１０の整数である。）
で表される分子構造を有するものが好ましい。

(Wherein R ¹ is an aliphatic hydrocarbon group which may have any of an ether bond site, a carbonyl group and a hydroxyl group. R ² is a polar group or a structural site having a polar group. R ³ Is a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, or an aryl group which may have a substituent, where n is an integer of 2 to 10.)
What has the molecular structure represented by these is preferable.

R ² in the structural formula (1) is a polar group or a structural moiety having a polar group. As described above, the substitution position on the aromatic ring of R ² is not particularly limited. However, since the calixarene compound (B) is further excellent in performance as a dispersant for the semiconductor nanocrystal (A), the para-position of R ¹ It is preferable to be located at.

  Examples of the polar group include a hydroxyl group, an amino group, a carboxy group, a thiol group, a phosphoric acid group, a phosphonic acid group, a phosphinic acid group, a phosphine oxide group, and an alkoxysilyl group. In the structural part having the polar group, the structural part other than the polar group is not particularly limited, and may have any structure. Specific examples of the structural moiety having a polar group include those represented by —O—X—P when the polar group is represented by P. X represents, for example, an alkylene group which may have a substituent, a (poly) alkylene ether structure, a (poly) alkylene thioether structure, a (poly) ester structure, a (poly) urethane structure, or a combination thereof. A site | part etc. are mentioned. Among these, an alkylene group is preferable, and an alkylene group having 1 to 6 carbon atoms is more preferable. Therefore, as a preferable example of the structural moiety having a polar group, a structural moiety represented by any one of the following structural formulas (2-1) to (2-7) can be given.

（式中Ｒ^４はそれぞれ独立に炭素原子数１〜６のアルキレン基である。Ｒ^５は炭素数１〜３のアルキル基である。）

(In the formula, each R ⁴ is independently an alkylene group having 1 to 6 carbon atoms. R ⁵ is an alkyl group having 1 to 3 carbon atoms.)

R ³ in the structural formula (1) is any one of a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, and an aryl group which may have a substituent. Specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, alkyl group of nonyl group, etc. An aliphatic hydrocarbon group, or a structural site in which one or more of the hydrogen atoms of the aliphatic hydrocarbon group are substituted with a hydroxyl group, an alkoxy group, a halogen atom, or the like; a phenyl group, a tolyl group, a xylyl group, a naphthyl group, an anthryl group And an aromatic ring-containing hydrocarbon group such as a group, and a structural site in which a hydroxyl group, an alkyl group, an alkoxy group, a halogen atom, or the like is substituted on the aromatic nucleus. Among these, R ³ is preferably a hydrogen atom.

  The calixarene compound (B) may be produced by any method and can be produced by various methods. Hereinafter, an example of a method for producing the calixarene compound (B) will be described.

For example, the calixarene compound (B) obtains an intermediate (α) represented by the following structural formula (3), and R ² in the structural formula (1) is added to the phenolic hydroxyl group of the intermediate (α). It can manufacture by the method of introduce | transducing the polar site | part or the structural site | part which has a polar group.

（式中Ｒ^１は脂肪族炭化水素基である。Ｒ^３は水素原子、置換基を有していてもよい脂肪族炭化水素基、置換基を有していてもよいアリール基の何れかである。ｎは２〜１０の整数である。）

(Wherein R ¹ is an aliphatic hydrocarbon group. R ³ is either a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, or an aryl group which may have a substituent. N is an integer from 2 to 10.)

  The method for producing the intermediate (α) was obtained by, for example, a method (Method 1-1) in which a phenol compound having an aliphatic hydrocarbon group and an aldehyde compound were directly reacted (Method 1-1) or Method 1-1. Examples thereof include a method (Method 1-2) in which the intermediate (α) is once dealkylated and then introduced again with an aliphatic hydrocarbon group (Method 1-2). Usually, it is convenient and preferable to produce by the above method 1-1. However, when it is difficult to obtain a phenol compound having a desired aliphatic hydrocarbon group, it is produced by the above method 1-2. Can do.

Regarding the method 1-1, the phenol compound used is not particularly limited as long as it is a phenol compound having one aliphatic hydrocarbon group corresponding to R ¹ in the structural formulas (1) and (3). May be used. As described above, R ¹ is preferably an aliphatic hydrocarbon group having 3 to 6 carbon atoms, and R ¹ and R ² in the structural formula (1) are located at a para position on the aromatic ring. Therefore, the phenol compound is preferably any one of parapropylphenol, parabutylphenol, parapentylphenol, and parahexylphenol.

  The aldehyde compound only needs to be capable of forming a calixarene structure by causing a condensation reaction with the phenol compound. For example, in addition to formaldehyde, aliphatic aldehyde compounds such as acetaldehyde and propionaldehyde; benzaldehyde, naphthaldehyde and the like An aromatic aldehyde compound etc. are mentioned. These may be used alone or in combination of two or more. Among them, it is preferable to use formaldehyde because of excellent reactivity. Formaldehyde may be used either as formalin in an aqueous solution or as paraformaldehyde in a solid state.

  Since the reaction ratio of the phenol compound and the aldehyde compound can produce the intermediate (α) in a high yield, the aldehyde compound may be in the range of 0.6 to 2 mol with respect to 1 mol of the phenol compound. preferable.

  The reaction between the phenol compound and the aldehyde compound can be performed, for example, at a temperature of about 80 to 250 ° C. in the presence of an acid or base catalyst. Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, organic acids such as methanesulfonic acid, paratoluenesulfonic acid, and oxalic acid, and Lewis acids such as boron trifluoride, anhydrous aluminum chloride, and zinc chloride. Is mentioned. These may be used alone or in combination of two or more. The addition amount of the acid catalyst is preferably in the range of 0.05 to 10 parts by mass with respect to 100 parts by mass in total of the phenol compound and the aldehyde compound. The base catalyst acts as a catalyst and is not particularly limited. Examples thereof include sodium hydroxide and potassium hydroxide. Examples thereof include alkali metal hydroxides such as rubidium hydroxide, and alkali metal carbonates such as sodium carbonate and potassium carbonate. These may be used alone or in combination of two or more. It is preferable that the addition amount of a base catalyst is 0.01-1 mass part with respect to a total of 100 mass parts of the said phenol compound and an aldehyde compound.

  The reaction between the phenol compound and the aldehyde compound may be performed in an organic solvent. Examples of the organic solvent include ester solvents such as ethyl acetate, methyl acetate, butyl acetate, methyl lactate, ethyl lactate, and butyl lactate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, and cyclohexane; methanol , Ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, ethyl hexanol, and other alcohol solvents; dimethyl ether, diethyl ether, isopropyl ether, methyl cellosolve, cellosolve, butyl cellosolve, THF, dioxane, butylcarbi Examples include ether solvents such as Tol and biphenyl ether; alcohol ether solvents such as methoxyethanol, ethoxyethanol and butoxyethanol. These may be used alone or in combination of two or more.

  In the method 1-2, the dealkylation step of the intermediate (α) includes, for example, the intermediate (α) in an organic solvent that is a poor solvent for the intermediate (α) and is a good solvent for phenol. ) And phenol, and aluminum chloride is added thereto and stirred. Examples of the organic solvent include aromatic hydrocarbon solvents such as benzene, alkylbenzene such as toluene and xylene, and the like. The amount of phenol added is preferably in the range of 1 to 2 mol with respect to 1 mol of the hydroxyl group in the intermediate (α). Moreover, it is preferable that the addition amount of an aluminum chloride is the range of 1-2 mol with respect to 1 mol of hydroxyl groups in the said intermediate body ((alpha)). The reaction is preferably performed under an ice bath or room temperature.

  Next, the method for introducing an aliphatic hydrocarbon group includes, for example, a method in which a target aliphatic hydrocarbon group is reacted with a carboxylic acid halide having the same carbon number to introduce an alkylcarbonyl group, and then the carbonyl group is reduced. Can be mentioned.

  The reaction between the dealkylated product of the intermediate (α) and the carboxylic acid halide can be carried out, for example, by a method in which both are stirred in the presence of aluminum chloride and a large excess of nitrobenzene. The addition amount of the carboxylic acid halide is preferably in the range of 1 to 3 moles with respect to 1 mole of the phenolic hydroxyl group contained in the dealkylated product of the intermediate (α). Moreover, it is preferable that the addition amount of an aluminum chloride is the range of 1-2 mol with respect to 1 mol of hydroxyl groups in the dealkylated substance of the said intermediate body ((alpha)). The reaction is preferably performed under an ice bath or room temperature.

  The reduction of the carbonyl group can be carried out by a method such as Clementen reduction or Wolf-Kishner reduction.

The method for introducing a polar group corresponding to R ² in the structural formula (1) or a structural part having a polar group into the phenolic hydroxyl group of the intermediate (α) varies depending on the type of structure to be introduced, and is diverse. Such a method can be exemplified, but any method may be used. Hereinafter, three main examples will be described.

Method 2-1: Method of reacting a halide having a structural portion corresponding to R ² Specifically, the intermediate (α) and the halogen are reacted under basic catalytic conditions in the same manner as in the so-called Williamson ether synthesis. React with the compound. As for the reaction ratio of both, it is preferable to use a halide in the range of 2 to 5 mol with respect to 1 mol of the phenolic hydroxyl group of the intermediate (α) since the reaction proceeds efficiently. The reaction may be carried out in an organic solvent. In particular, the reaction proceeds more efficiently by reacting in a polar solvent such as N-dimethylformamide, N-dimethylacetamide or tetrahydrofuran.

The halide may have a structural site corresponding to R ^{2 as} it is, or may be a compound capable of deriving a structural site corresponding to R ² . For example, when R ² is a structural moiety having an amino group, a method in which a halide having a phthalimide group is reacted and then aminated by Gabriel amine synthesis is exemplified. Further, when R ² is a structural moiety having a phosphonic acid group, a method of reacting a halide having a phosphonic acid ester group and then hydrolyzing it into a phosphonic acid group can be mentioned.

Method 2-2: A method in which an allyl halide is reacted to form an allyl ether, and then a compound having a structural moiety corresponding to R ² is added to an allyl group.
The allyl etherification reaction with an allyl halide can be carried out in the same manner as in the above method 2-1, by using an allyl halide in place of the halide used in the above method 2-1.

The addition reaction to the allyl group can be performed in the same manner as a general nucleophilic substitution reaction. Further, the compound to be added to the allyl group may have a structural site corresponding to R ² as it is, or may be a compound capable of inducing a structural site corresponding to R ² . For example, when R ² is a structural moiety having a thiol group, a method of adding thioacetic acid and then deacetylating it to obtain a thiol group can be mentioned.

  In the present invention, a compound (B ′) other than the calixarene compound (B) may be used as a surface modifier or dispersant for the semiconductor nanocrystal (A). The compound (B ′) only needs to have a chemical structure that can function as a surface modifier or dispersant for the semiconductor nanocrystal (A), and specifically includes a hydroxyl group, a thiol group, a carboxy group, and phosphoric acid. And a compound having a polar group such as a group, a phosphonic acid group, a phosphinic acid group, a phosphine oxide group, and an alkoxysilyl group and a hydrocarbon structure site having an affinity for an organic solvent or a resin component. Such a compound (B ′) is, for example, a trialkylphosphine oxide such as trioctylphosphine oxide; lauric acid, myristic acid, pentadecylic acid, palmitic acid, palmitoleic acid, margaric acid, stearic acid, oleic acid, vaccenic acid, Long-chain fatty acids such as linoleic acid, linolenic acid, eleostearic acid, arachidic acid, and arachidonic acid; long-chain alkylamines such as dodecylamine, tetradecylamine, hexadecylamine, and octadecylamine. These may be used alone or in combination of two or more. When these compounds (B ′) are used, the ratio with the calixarene compound (B) is not particularly limited, and desired performance in the surface-modified semiconductor nanocrystals, or an organic solvent used by mixing the surface-modified semiconductor nanocrystals Or it can adjust suitably according to the kind etc. of resin material.

  The surface-modified semiconductor nanocrystal of the present invention is obtained by modifying the surface of the semiconductor nanocrystal (A) with the calixarene compound (B). The manufacturing method is not particularly limited, and any method may be used. Hereinafter, an example of a method for producing the surface-modified semiconductor nanocrystal of the present invention will be described.

  First, core particles of the semiconductor nanocrystal (A) are manufactured. The manufacturing method of the core particle of the semiconductor nanocrystal (A) is not particularly limited, and can be manufactured by various methods including a known manufacturing method. Examples of the production method include a wet chemical method (also called a hot soap method), a metal organic chemical vapor deposition method, a molecular beam epitaxy method, a sol-gel method, and the like. Especially, since it becomes a semiconductor nanocrystal (A) excellent in a light emission characteristic and a dispersibility, it is preferable to manufacture a core particle by the said wet chemical method.

  Specifically, the wet chemical method is a method in which the raw material of the semiconductor compound (1) contained in the core particles is put into a high-temperature organic solvent at about 150 to 350 ° C. to grow crystal particles. The raw material of the semiconductor compound (1) is appropriately selected according to the desired semiconductor compound (1). For example, when the semiconductor compound (1) is InP, a combination of an In source such as indium acetate and a P source such as tris (trialkylsilyl) phosphine can be used. In the case of CdSe, a combination of a Cd source such as dimethylcadmium or cadmium oxide and a Se source such as Se powder can be used. Moreover, the organic solvent to be used is suitably selected according to the solubility of the said raw material, reaction temperature, etc. The average particle diameter of the core particles is preferably about 1 nm to 20 nm. The average particle diameter of the core particles, semiconductor nanocrystals (A), and surface-modified semiconductor nanocrystals can be directly observed by using a transmission electron microscope (TEM) or a scanning electron microscope (SEM). The values are obtained by a method of obtaining from the ratio of major axis to minor axis by a projected two-dimensional image, measurement by a light scattering method, measurement by a sedimentation type particle size measurement method using a solvent, or the like.

  Next, a shell that covers at least a part of the core particles is formed to form the semiconductor nanocrystal (A) and to obtain a surface-modified semiconductor nanocrystal. The method for forming the shell is not particularly limited, and the shell can be manufactured by various methods. Especially, since it becomes a semiconductor nanocrystal (A) excellent in a light emission characteristic and a dispersibility, it is preferable to form by a wet chemical method similarly to manufacture of the said core particle. Specifically, it is a method in which the core particles obtained above and the raw material of the semiconductor material (2) contained in the shell are put into a high-temperature organic solvent at about 150 to 350 ° C. to grow crystal particles. When the shell has a multilayer structure, the shells may be formed one by one in order or may be formed at a time by introducing raw materials all at once. The raw material of the semiconductor compound (2) is appropriately selected according to the desired semiconductor compound (2). For example, when the semiconductor compound (2) is ZnS, a zinc source such as dialkyl zinc, zinc oxide, fatty acid zinc and zinc acetate and a sulfur source such as thioacetamide, bis (trimethylsilyl) and sulfide element sulfur A combination etc. are mentioned. Moreover, the organic solvent to be used is suitably selected according to the solubility of the said raw material, reaction temperature, etc.

  The calixarene compound (B) and the compound (B ′) may be added at the core particle production stage or at the shell formation stage. Moreover, the addition amount is not specifically limited, It adjusts suitably by the kind of dispersion medium, the desired performance in the surface modification semiconductor nanocrystal obtained, etc. Among these, the surface-modified semiconductor nanocrystals can be efficiently and stably produced, and therefore, it is preferable to add them at both the core particle production stage and the shell formation stage. The calixarene compound (B) is preferably added at the shell formation stage. The addition amount of the calixarene compound (B) or the compound (B ′) is preferably used in the range of 0.5 to 1000% by mass with respect to the total raw material mass of the semiconductor nanocrystal (A). The addition amount in the production stage of the core particles is in the range of 0.5 to 1000% by mass in total of the calixarene compound (B) and the compound (B ′) with respect to the total raw material mass of the semiconductor compound (1). It is preferable to use it. The addition amount in the shell formation stage is 0.5 to 1000 in total for the calixarene compound (B) and the compound (B ′) with respect to the total mass of the core particles and the raw material of the semiconductor compound (2). It is preferable to use in the range of mass%.

  The average particle diameter of the surface-modified semiconductor nanocrystal is preferably about 1 nm to 50 nm. Further, the fluorescence quantum yield of the surface-modified semiconductor nanocrystal is preferably 30% or more, and more preferably 40% or more. The full width at half maximum of the fluorescence spectrum of the surface-modified semiconductor nanocrystal is preferably 60 nm or less, and more preferably 45 nm or less.

The surface-modified semiconductor nanocrystal of the present invention can be used for a wide variety of applications without particular limitation. Since the Alixarene compound (B) has a plurality of adsorption points to the semiconductor nanocrystal (A), the adsorption force to the semiconductor nanocrystal (A) is stronger than that of a generally known surface modifier. Therefore, the surface of the semiconductor nanocrystal (A) can be coated even with a relatively small amount of use. In addition, since a bulky calixarene structure exists between the R ¹ group and the R ² group, the surface modifier is not adsorbed on the surface of the semiconductor nanocrystal (A) in multiple layers, and the minimum necessary surface modification Only the agent can be adsorbed on the surface of the semiconductor nanocrystal (A). Therefore, the surface-modified light-emitting nanocrystal of the present invention is very excellent in dispersion stability in various organic solvents and resin materials, and at the same time, even when the semiconductor nanocrystal (A) concentration is increased, the film properties are excellent, and the fluorescence From the standpoint of quantum yield or luminous efficiency, it exhibits extremely excellent performance.

  A wide variety of organic solvents can be used without any particular limitation. Specific examples include alkyl monoalcohol solvents such as methanol, ethanol, and propanol; ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1, Alkyl polyol solvents such as 6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, trimethylene glycol, diethylene glycol, polyethylene glycol, glycerin; 2-ethoxyethanol, ethylene glycol monomethyl Ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monopentyl ether, ethylene glycol dimethyl ether Alkylene glycol monoalkyl ether solvents such as ethylene glycol ethyl methyl ether, ethylene glycol monophenyl ether, propylene glycol monomethyl ether; dialkylene glycol dialkyl ether solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether; Alkylene glycol alkyl ether acetate solvents such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate; 1,3-dioxane, 1,4-dioxane, tetrahydrofuran, cyclopentyl methyl ether, etc. Ether solvents; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl amyl ketone; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate , Ethyl oxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl formate, ethyl acetate, butyl acetate, methyl acetoacetate, ethyl acetoacetate, etc. Solvent: Aromatic hydrocarbon solvents such as benzene, toluene, xylene and the like.

  The surface-modified semiconductor nanocrystal of the present invention can be used for a wide variety of applications without particular limitation. Applications of the surface-modified semiconductor nanocrystals of the present invention include, for example, display display field, electric / electronic device field, fluorescent ink, coating agent, lens, bio fluorescent probe, and the like. More specifically, the display display field includes color filters, backlights, wavelength conversion films, and the like. In the electric / electronic device field, more specifically, LED, photovoltaic power generation, solar cell, semiconductor laser, light receiving sensor, wavelength conversion element, light-light conversion element, and the like can be mentioned.

In the various applications, the surface-modified semiconductor nanocrystals are generally used mainly dispersed in a resin material. The method for dispersing the surface-modified semiconductor nanocrystals in the resin material is not particularly limited, for example, a method of directly mixing in a resin material, a method of mixing a solvent solution of the surface-modified semiconductor nanocrystals with a resin, Examples thereof include a method of collectively mixing the surface-modified semiconductor nanocrystal, the organic solvent, and the resin material. The solvent may be removed after the composition containing the surface-modified semiconductor nanocrystal, the organic solvent, and the resin material is once prepared.
The resin material can be appropriately selected according to each application, but basically needs to have light transmittance. In the case of a curable resin material, it is sufficient if the cured product has light transmittance even if the state before curing is somewhat turbid. Examples of such resin materials include active energy ray-curable resin materials such as (meth) acrylate compounds and oxetane compounds; thermosetting resin materials such as epoxy resins and polyester resins; acrylic resins, cellulose resins, polyester resins, and cycloolefins. Examples thereof include thermoplastic resin materials such as thermoplastic resins such as resin, polystyrene resin, polyethylene resin, polypropylene resin, and polycarbonate resin. The resin material in which the surface-modified semiconductor nanocrystals are dispersed is printed on a substrate by a method such as inkjet printing, laser printing, screen printing, offset printing, relief printing, gravure printing, flexographic printing, bar coating, spin coating, or the like. A desired application can be obtained by a method of applying and curing as appropriate, or a method of shaping using a mold.

  Among the application uses of semiconductor nanocrystals, color filter use is mentioned as being widely studied. Examples of the method for producing the color filter include a photolithography method and an ink jet method. In particular, from the viewpoint of simplifying the production process, production by an ink jet method is preferable. Hereinafter, as an example of a method for using the surface-modified semiconductor nanocrystal of the present invention, the production of a color filter by an ink jet method using the same will be briefly described.

  When the surface-modified semiconductor nanocrystal is used for manufacturing a color filter by an inkjet method, an active energy ray-curable resin material or a thermosetting resin material is used as the resin material. The inkjet resin composition when the active energy ray-curable resin material is used as the resin material is the composition (1), and the inkjet resin composition when the thermosetting resin material is used as the resin material is the composition ( 2).

  About the said composition (1), various (meth) acrylate compounds are mentioned as said active energy ray curable resin material. Specifically, various (meth) acrylate compounds include mono (meth) acrylate compounds and modified products (R1), aliphatic hydrocarbon type poly (meth) acrylate compounds and modified products (R2), and alicyclic compounds. Poly (meth) acrylate compound and modified product (R3), aromatic poly (meth) acrylate compound and modified product (R4), (meth) acrylate resin having silicone chain and modified product (R5), epoxy (meta) ) Acrylate resin and its modified body (R6), urethane (meth) acrylate resin and its modified body (R7), acrylic (meth) acrylate resin and its modified body (R8), dendrimer type (meth) acrylate resin and its modified body (R9) etc. are mentioned.

  Examples of the mono (meth) acrylate compound and the modified product (R1) include methyl (meth) acrylate, ethyl (meth) acrylate, hydroxyethyl (meth) acrylate, propyl (meth) acrylate, hydroxypropyl (meth) acrylate, Aliphatic mono (meth) acrylate compounds such as butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate; alicyclic mono (meta) such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate and adamantyl mono (meth) acrylate ) Acrylate compounds; heterocyclic mono (meth) acrylate compounds such as glycidyl (meth) acrylate and tetrahydrofurfuryl acrylate; phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxy (Meth) acrylate, phenoxyethyl (meth) acrylate, phenoxyethoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, phenylphenol (meth) acrylate, phenylbenzyl (meth) acrylate, phenoxybenzyl ( Aromatic mono (meth) acrylate compounds such as meth) acrylate, benzylbenzyl (meth) acrylate, phenylphenoxyethyl (meth) acrylate, paracumylphenol (meth) acrylate; structural formula (4)

（式中Ｒ^４は水素原子又はメチル基である。）
で表される化合物等のモノ（メタ）アクリレート化合物：前記各種のモノ（メタ）アクリレート化合物の分子構造中に（ポリ）オキシエチレン鎖、（ポリ）オキシプロピレン鎖、（ポリ）オキシテトラメチレン鎖等の（ポリ）オキシアルキレン鎖を導入した（ポリ）オキシアルキレン変性体；前記各種のモノ（メタ）アクリレート化合物の分子構造中に（ポリ）ラクトン構造を導入したラクトン変性体等が挙げられる。

(In the formula, R ⁴ is a hydrogen atom or a methyl group.)
Mono (meth) acrylate compounds such as compounds represented by: (poly) oxyethylene chain, (poly) oxypropylene chain, (poly) oxytetramethylene chain, etc. in the molecular structure of the various mono (meth) acrylate compounds (Poly) oxyalkylene-modified products in which a (poly) oxyalkylene chain is introduced; lactone-modified products in which a (poly) lactone structure is introduced into the molecular structure of the various mono (meth) acrylate compounds.

  Examples of the aliphatic hydrocarbon type poly (meth) acrylate compound and the modified product (R2) include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butanediol di (meth) acrylate, and hexanediol diene. Aliphatic di (meth) acrylate compounds such as (meth) acrylate and neopentyl glycol di (meth) acrylate; trimethylolpropane tri (meth) acrylate, glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylol Aliphatic tri (meth) acrylate compounds such as propane tri (meth) acrylate and dipentaerythritol tri (meth) acrylate; pentaerythritol tetra (meth) acrylate and ditrimethylol group Tetra- or higher functional aliphatic poly (meth) acrylate compounds such as pantetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate; (Poly) oxyalkylene chains such as (poly) oxyethylene chain, (poly) oxypropylene chain, and (poly) oxytetramethylene chain are introduced into the molecular structure of the aliphatic hydrocarbon type poly (meth) acrylate compound (poly ) Oxyalkylene modified products; lactone modified products in which a (poly) lactone structure is introduced into the molecular structure of the above-mentioned various aliphatic hydrocarbon type poly (meth) acrylate compounds.

  The alicyclic poly (meth) acrylate compound and the modified product (R3) are, for example, 1,4-cyclohexanedimethanol di (meth) acrylate, norbornane di (meth) acrylate, norbornane dimethanol di (meth) acrylate, Alicyclic di (meth) acrylate compounds such as dicyclopentanyl di (meth) acrylate and tricyclodecane dimethanol di (meth) acrylate; in the molecular structure of the various alicyclic poly (meth) acrylate compounds ( (Poly) oxyalkylene chain such as (poly) oxyethylene chain, (poly) oxypropylene chain, (poly) oxytetramethylene chain, etc.) (poly) oxyalkylene modified product; various alicyclic poly (meth) acrylates described above Lactone modification by introducing (poly) lactone structure into the molecular structure of the compound Etc. The.

  Examples of the aromatic poly (meth) acrylate compound and the modified product (R4) include biphenol di (meth) acrylate, bisphenol di (meth) acrylate, and the following structural formula (5).

［式中Ｒ^５はそれぞれ独立に（メタ）アクリロイル基、（メタ）アクリロイルオキシ基、（メタ）アクリロイルオキシアルキル基の何れかである。］
で表されるビカルバゾール化合物、下記構造式（６−１）又は（６−２）

[In the formula, each R ⁵ independently represents any of a (meth) acryloyl group, a (meth) acryloyloxy group, and a (meth) acryloyloxyalkyl group. ]
A bicarbazole compound represented by the following structural formula (6-1) or (6-2)

［式中Ｒ^５はそれぞれ独立に（メタ）アクリロイル基、（メタ）アクリロイルオキシ基、（メタ）アクリロイルオキシアルキル基の何れかである。］
で表されるフルオレン化合物等の芳香族ジ（メタ）アクリレート化合物；前記各種の芳香族ポリ（メタ）アクリレート化合物の分子構造中に（ポリ）オキシエチレン鎖、（ポリ）オキシプロピレン鎖、（ポリ）オキシテトラメチレン鎖等の（ポリ）オキシアルキレン鎖を導入した（ポリ）オキシアルキレン変性体；前記各種の芳香族ポリ（メタ）アクリレート化合物の分子構造中に（ポリ）ラクトン構造を導入したラクトン変性体等が挙げられる。

[In the formula, each R ⁵ independently represents any of a (meth) acryloyl group, a (meth) acryloyloxy group, and a (meth) acryloyloxyalkyl group. ]
An aromatic di (meth) acrylate compound such as a fluorene compound represented by: (poly) oxyethylene chain, (poly) oxypropylene chain, (poly) in the molecular structure of the various aromatic poly (meth) acrylate compounds (Poly) oxyalkylene modified products in which (poly) oxyalkylene chains such as oxytetramethylene chains are introduced; lactone modified products in which (poly) lactone structures are introduced into the molecular structures of the various aromatic poly (meth) acrylate compounds Etc.

  The (meth) acrylate resin having a silicone chain and the modified product (R5) thereof are not particularly limited as long as they are compounds having a silicone chain and a (meth) acryloyl group in the molecular structure. Good. Moreover, the manufacturing method is not particularly limited. Specific examples of the (meth) acrylate resin having a silicone chain and the modified product (R5) include, for example, a reaction product of a silicone compound having an alkoxysilane group and a hydroxyl group-containing (meth) acrylate compound.

  Examples of commercially available silicone compounds having an alkoxysilane group include, for example, “X-40-9246” (alkoxy group content 12 mass%), “KR-9218” (alkoxy group-containing) manufactured by Shin-Etsu Chemical Co., Ltd. 15 mass%), “X-40-9227” (alkoxy group-containing 15 mass%), “KR-510” (alkoxy group content 17 mass%), “KR-213” (alkoxy group content 20 mass%) ), "X-40-9225" (alkoxy group content 24 mass%), "X-40-9250" (alkoxy group content 25 mass%), "KR-500" (alkoxy group content 28 mass%) , "KR-401N" (alkoxy group content 33% by mass), "KR-515" (alkoxy group content 40% by mass), "KC-89S" (alkoxy group content 45 quality) %), And the like. These may be used alone or in combination of two or more. Especially, it is preferable that alkoxy group content is the range of 15-40 mass%. Moreover, when using 2 or more types together as a silicone compound, it is preferable that the average value of each alkoxy group content is the range of 15-40 mass%.

  Examples of the hydroxyl group-containing (meth) acrylate compound include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, and ditrimethylolpropane tri (meth). Hydroxyl group-containing (meth) acrylate compounds such as acrylate and dipentaerythritol penta (meth) acrylate; in the molecular structure of the various hydroxyl group-containing (meth) acrylate compounds, (poly) oxyethylene chain, (poly) oxypropylene chain, ( (Poly) oxyalkylene chain such as poly) oxytetramethylene chain modified (poly) oxyalkylene modified product; (poly) lactone structure is introduced into the molecular structure of the above various hydroxyl group-containing (meth) acrylate compounds Lactone-modified products thereof.

  Further, as the (meth) acrylate resin having the silicone chain and the modified product (R5), “X-22-174ASX” (methacryloyl) manufactured by Shin-Etsu Chemical Co., Ltd., which is a silicone oil having a (meth) acryloyl group at one end. Group equivalent 900 g / equivalent), “X-22-174BX” (methacryloyl group equivalent 2,300 g / equivalent), “X-22-174DX” (methacryloyl group equivalent 4,600 g / equivalent), “KF-2012” (methacryloyl) Group equivalent 4,600 g / equivalent), "X-22-2426" (methacryloyl group equivalent 12,000 g / equivalent), "X-22-2404" (methacryloyl group equivalent 420 g / equivalent), "X-22-2475" (Methacryloyl group equivalent 420 g / equivalent); a silicone oil having (meth) acryloyl groups at both ends "X-22-164" (methacryloyl group equivalent 190 g / equivalent), "X-22-164AS" (methacryloyl group equivalent 450 g / equivalent), "X-22-164A" (methacryloyl group equivalent) 860 g / equivalent), “X-22-164B” (methacryloyl group equivalent 1,600 g / equivalent), “X-22-164C” (methacryloyl group equivalent 2,400 g / equivalent), “X-22-164E” (methacryloyl) Group equivalent 3,900 g / equivalent), "X-22-2445" (acryloyl group equivalent 1,600 g / equivalent); Shin-Etsu Chemical Co., Ltd., which is an oligomeric silicone compound having a plurality of (meth) acryloyl groups in one molecule “KR-513” (methacryloyl group equivalent 210 g / equivalent), “-40-9296” (methacryloyl group equivalent 230 / Equivalent), “AC-SQ TA-100” manufactured by Toagosei Co., Ltd. (acryloyl group equivalent 165 g / equivalent), “AC-SQ SI-20” (acryloyl group equivalent 207 g / equivalent), “MAC-SQ TM-100 ”(Methacryloyl group equivalent 179 g / equivalent),“ MAC-SQ SI-20 ”(methacryloyl group equivalent 224 g / equivalent),“ MAC-SQ HDM ”(methacryloyl group equivalent 239 g / equivalent) may be used. .

  The (meth) acrylate resin having a silicone chain and the modified product (R5) preferably have a weight average molecular weight (Mw) in the range of 1,000 to 10,000, and in the range of 1,000 to 5,000. Is more preferable. Further, the (meth) acryloyl group equivalent is preferably in the range of 150 to 5,000 g / equivalent, and more preferably in the range of 150 to 2,500 g / equivalent.

  As for the said epoxy (meth) acrylate resin and its modified body (R6), what is obtained by making (meth) acrylic acid or its anhydride react with an epoxy resin is mentioned, for example. Examples of the epoxy resin include diglycidyl ethers of dihydric phenols such as hydroquinone and catechol; diglycidyl ethers of biphenol compounds such as 3,3′-biphenyldiol and 4,4′-biphenyldiol; bisphenol A type epoxy resins; Bisphenol type epoxy resins such as bisphenol B type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin; 1,4-naphthalenediol, 1,5-naphthalenediol, 1,6-naphthalenediol, 2,6-naphthalene Polyglycidyl ethers of naphthol compounds such as diols, 2,7-naphthalenediol, binaphthol, bis (2,7-dihydroxynaphthyl) methane; triglycidyl ethers such as 4,4 ′, 4 ″ -methylidynetrisphenol A novolak type epoxy resin such as a phenol novolak type epoxy resin or a cresol novolak resin; a molecular structure of the various epoxy resins such as a (poly) oxyethylene chain, a (poly) oxypropylene chain, a (poly) oxytetramethylene chain, etc. (Poly) oxyalkylene chain-modified (poly) oxyalkylene-modified products; lactone-modified products in which (poly) lactone structures are introduced into the molecular structures of the various epoxy resins.

  Examples of the urethane (meth) acrylate resin and the modified product (R7) include those obtained by reacting various polyisocyanate compounds, hydroxyl group-containing (meth) acrylate compounds, and various polyol compounds as necessary. It is done. Examples of the polyisocyanate compound include aliphatic diisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate; norbornane diisocyanate, isophorone diisocyanate, hydrogenated Alicyclic diisocyanate compounds such as xylylene diisocyanate and hydrogenated diphenylmethane diisocyanate; aromatic diisocyanate compounds such as tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate; 7) Polymethylene polyphenyl polyi having a repeating structure represented by Cyanate; These isocyanurate modified product, a biuret modified product, and allophanate modified compounds and the like.

［式中、Ｒ^６はそれぞれ独立に水素原子、炭素原子数１〜６の炭化水素基の何れかである。Ｒ^７はそれぞれ独立に炭素原子数１〜４のアルキル基、又は構造式（７）で表される構造部位と＊印が付されたメチレン基を介して連結する結合点の何れかである。ｑは０又は１〜３の整数であり、ｐは１以上の整数である。］

[Wherein, R ⁶ is independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. R ⁷ is each independently an alkyl group having 1 to 4 carbon atoms, or a bonding point that is linked to a structural moiety represented by the structural formula (7) via a methylene group marked with *. q is 0 or an integer of 1 to 3, and p is an integer of 1 or more. ]

  Examples of the hydroxyl group-containing (meth) acrylate compound include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, and ditrimethylolpropane tri (meth). Hydroxyl group-containing (meth) acrylate compounds such as acrylate and dipentaerythritol penta (meth) acrylate; in the molecular structure of the various hydroxyl group-containing (meth) acrylate compounds, (poly) oxyethylene chain, (poly) oxypropylene chain, ( (Poly) oxyalkylene chain such as poly) oxytetramethylene chain modified (poly) oxyalkylene modified product; (poly) lactone structure is introduced into the molecular structure of the above various hydroxyl group-containing (meth) acrylate compounds Lactone-modified products thereof.

  Examples of the polyol compound include aliphatic polyol compounds such as ethylene glycol, propylene glycol, butanediol, hexanediol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol; aromatics such as biphenol and bisphenol. (Poly) oxyalkylene in which (poly) oxyethylene chain, (poly) oxypropylene chain, (poly) oxytetramethylene chain, or other (poly) oxyalkylene chain is introduced into the molecular structure of the various polyol compounds. Modified body: lactone modified body in which a (poly) lactone structure is introduced into the molecular structure of the various polyol compounds.

  The acrylic (meth) acrylate resin and the modified product (R8) are polymerized using, for example, a (meth) acrylate monomer (α) having a reactive functional group such as a hydroxyl group, a carboxy group, an isocyanate group, or a glycidyl group as an essential component. Obtained by introducing a (meth) acryloyl group by further reacting a (meth) acrylate monomer (β) having a reactive functional group capable of reacting with these functional groups into an acrylic resin intermediate obtained by Is mentioned.

  The (meth) acrylate monomer (α) having a reactive functional group is, for example, a hydroxyl group-containing (meth) acrylate monomer such as hydroxyethyl (meth) acrylate or hydroxypropyl (meth) acrylate; a carboxy such as (meth) acrylic acid Group-containing (meth) acrylate monomer; isocyanate group-containing (meth) acrylate monomer such as 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, 1,1-bis (acryloyloxymethyl) ethyl isocyanate; glycidyl (meth) acrylate And glycidyl group-containing (meth) acrylate monomers such as 4-hydroxybutyl acrylate glycidyl ether. These may be used alone or in combination of two or more.

  In addition to the (meth) acrylate monomer (α), the acrylic resin intermediate may be obtained by copolymerizing another polymerizable unsaturated group-containing compound as necessary. Examples of the other polymerizable unsaturated group-containing compound include (meth) methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like. Acrylic acid alkyl ester; Cyclo ring-containing (meth) acrylate such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate; phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl acrylate Aromatic ring-containing (meth) acrylates; silyl group-containing (meth) acrylates such as 3-methacryloxypropyltrimethoxysilane; styrene derivatives such as styrene, α-methylstyrene, and chlorostyrene . These may be used alone or in combination of two or more.

  The (meth) acrylate monomer (β) is not particularly limited as long as it can react with the reactive functional group of the (meth) acrylate monomer (α), but is the following combination from the viewpoint of reactivity. Is preferred. That is, when the hydroxyl group-containing (meth) acrylate is used as the (meth) acrylate monomer (α), it is preferable to use an isocyanate group-containing (meth) acrylate as the (meth) acrylate monomer (β). When the carboxy group-containing (meth) acrylate is used as the (meth) acrylate monomer (α), it is preferable to use the glycidyl group-containing (meth) acrylate as the (meth) acrylate monomer (β). When the isocyanate group-containing (meth) acrylate is used as the (meth) acrylate monomer (α), the hydroxyl group-containing (meth) acrylate is preferably used as the (meth) acrylate monomer (β). When the glycidyl group-containing (meth) acrylate is used as the (meth) acrylate monomer (α), the carboxy group-containing (meth) acrylate is preferably used as the (meth) acrylate monomer (β).

  The acrylic (meth) acrylate resin and the modified product (R8) preferably have a weight average molecular weight (Mw) in the range of 5,000 to 50,000. The (meth) acryloyl group equivalent is preferably in the range of 200 to 300 g / equivalent.

  The dendrimer type (meth) acrylate resin and the modified product (R9) are a resin having a regular multi-branched structure and having a (meth) acryloyl group at the end of each branched chain. In addition, it is called a hyperbranch type or a star polymer. Examples of such a compound include those represented by the following structural formulas (8-1) to (8-8), but are not limited thereto, and have a regular multi-branched structure. Any resin can be used as long as it has a (meth) acryloyl group at the end of each branched chain.

（式中Ｒ^４は水素原子又はメチル基であり、Ｒ^８は炭素原子数１〜４の炭化水素基である。）

(Wherein R ⁴ is a hydrogen atom or a methyl group, and R ⁸ is a hydrocarbon group having 1 to 4 carbon atoms.)

  As such a dendrimer type (meth) acrylate resin and its modified body (R9), “Viscoat # 1000” manufactured by Osaka Organic Chemical Co., Ltd. [weight average molecular weight (Mw) 1,500 to 2,000, average per molecule (Meth) acryloyl group number 14], “Biscoat 1020” [weight average molecular weight (Mw) 1,000 to 3,000], “SIRIUS501” [weight average molecular weight (Mw) 15,000 to 23,000], manufactured by MIWON “SP-1106” [weight average molecular weight (Mw) 1,630, average (meth) acryloyl group number 18 per molecule], “CN2301”, “CN2302” [average (meth) acryloyl group number per molecule] 16], “CN2303” [average (meth) acryloyl group number 6 per molecule], “CN 304 "[average (meth) acryloyl group number 18 per molecule]," Esdrimer HU-22 "manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.," A-HBR-5 "manufactured by Shin-Nakamura Chemical Co., Ltd., manufactured by Daiichi Kogyo Seiyaku Co., Ltd. Commercial products such as “New Frontier R-1150” and “Hypertech UR-101” manufactured by Nissan Chemical Co., Ltd. may be used.

  The dendrimer type (meth) acrylate resin and the modified product (R9) preferably have a weight average molecular weight (Mw) in the range of 1,000 to 30,000. Moreover, what is the range whose average (meth) acryloyl group number per molecule is 5-30 is preferable.

  These (meth) acrylate compounds may be used alone or in combination of two or more. Among them, the mono (meth) acrylate compound and its modified product (R1), the aliphatic hydrocarbon type poly (meth) acrylate compound and its modified product (R2), the alicyclic poly (meth) acrylate compound and its modified product Body (R3), those having a relatively low molecular weight such as aromatic poly (meth) acrylate compound and modified body (R4), (meth) acrylate resin having silicone chain and modified body (R5), The epoxy (meth) acrylate resin and its modified product (R6), the urethane (meth) acrylate resin and its modified product (R7), the acrylic (meth) acrylate resin and its modified product (R8), the dendrimer type (meta ) Use in combination with relatively high molecular weight materials such as acrylate resins and their modified products (R9). It is preferred.

  The composition (1) may contain other resin components other than the (meth) acrylate compound. Other resin components are used for the purpose of adjusting the viscosity and improving the adhesion to the printing substrate. For example, acrylic resins such as methyl methacrylate resin and methyl methacrylate copolymer; polystyrene, methyl methacrylate-styrene Polyester resins; Polyurethane resins; Polybutadiene resins such as polybutadiene and butadiene-acrylonitrile copolymers; Epoxy resins such as bisphenol type epoxy resins, phenoxy resins and novolac type epoxy resins, and the like. When other resin components are used, it is preferably used at 20 parts by mass or less, more preferably at 10 parts by mass or less, with respect to 100 parts by mass of the (meth) acrylate compound.

  The composition (1) preferably contains a photopolymerization initiator. What is necessary is just to select and use the suitable photoinitiator by the kind etc. of the active energy ray to irradiate. Specific examples of the photopolymerization initiator include, for example, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2- (dimethylamino) Alkylphenone photopolymerization initiators such as 2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone; 2,4,6-trimethylbenzoyl-diphenyl- Examples include acylphosphine oxide photopolymerization initiators such as phosphine oxide; intramolecular hydrogen abstraction type photopolymerization initiators such as benzophenone compounds. These may be used alone or in combination of two or more.

  Commercially available products of the photopolymerization initiator include, for example, “IRGACURE127”, “IRGACURE184”, “IRGACURE250”, “IRGACURE270”, “IRGACURE290”, “IRGACURE369E”, “IRGACURE379EG”, “IRGACURE500”, “IRGACURE500”, manufactured by BASF. , “IRGACURE 754”, “IRGACURE 819”, “IRGACURE 907”, “IRGACURE 1173”, “IRGACURE 2959”, “IRGACURE MBF”, “IRGACURE TPO”, “IRGACURE OXE 01”, “IRGACURE OX etc.”

  The amount of the photopolymerization initiator used is preferably in the range of 0.05 to 20% by mass in the composition (1), and more preferably in the range of 0.1 to 10% by mass.

  The composition (1) may contain a polymerization inhibitor such as hydroquinone, methoquinone, di-t-butylhydroquinone, P-methoxyphenol, butylhydroxytoluene, nitrosamine salt, etc. in order to enhance storage stability. The addition amount of these polymerization inhibitors is preferably in the range of 0.01 to 2% by mass in the composition (1).

  The said composition (1) may contain the coloring material as needed. As the coloring material, a known coloring material can be used, for example, a red coloring material such as a diketopyrrolopyrrole pigment or an anionic red organic dye; a copper halide phthalocyanine pigment, a phthalocyanine green dye, or a phthalocyanine blue color. Examples thereof include green color materials such as dyes and azo yellow organic dyes; blue color materials such as ε-type copper phthalocyanine pigments and cationic blue organic dyes.

  The composition (1) may contain various additives as necessary. Examples of additives include UV absorbers, antioxidants, photosensitizers, silicone additives, silane coupling agents, fluorine additives, rheology control agents, defoaming agents, antistatic agents, and antifogging agents. , Adhesion aids, organic fillers, inorganic fillers and the like. The addition amount of these additives is preferably in the range of 0.05 to 20% by mass in the composition (1).

  Although the said composition (1) may contain a solvent as needed, it is preferable that the content rate of a solvent is small from viewpoints, such as a working environment. Specifically, the solvent content in the composition (1) is preferably 100 ppm or less, and preferably not substantially contained.

  The composition (1) is preferably designed so that its viscosity is 1-1000 mPa · sec. The viscosity is a value measured using a rotational viscometer (manufactured by Toki Sangyo Co., Ltd .: TVE-20L). Moreover, it is preferable that the surface tension of the said composition (1) is 20-50 mN / m, and it is more preferable that it is 30-50 mN / m.

  For the composition (2), examples of the thermosetting resin material include an epoxy compound. Specific examples of the epoxy compound include, for example, polyglycidyl ether (R10) of an aliphatic polyol compound, polyglycidyl ether (R11) of an aromatic polyol compound, a reaction product of various phenolic hydroxyl group-containing compounds and various aldehyde compounds. Examples thereof include polyglycidyl ether (R12), glycidyl group-containing acrylic resin (R13), glycidylamine compound (R14), and alicyclic structure-containing epoxy resin (R15).

  The polyglycidyl ether (R10) of the aliphatic polyol compound is, for example, ethylene glycol, propylene glycol, butanediol, hexanediol, neopentyl glycol, trimethylolpropane, glycerin, pentaerythritol, ditrimethylolpropane, dipentaerythritol, etc. Examples include polyglycidyl etherified products of aliphatic polyol compounds. The polyglycidyl ether (R10) may partially contain a ring-opening addition reaction product of an epoxy group and a hydroxyl group.

  Examples of the polyglycidyl ether (R11) of the aromatic polyol compound include dihydroxybenzene, dihydroxynaphthalene, biphenol, tetramethylbiphenol, bisphenol A, bisphenol, bisphenol F, bisphenol S, binaphthol, bis (dihydroxynaphthyl) methane, and triphenol. Examples thereof include polyglycidyl etherified products of aromatic polyol compounds such as methane. The polyglycidyl ether (R11) may partially contain a ring-opening addition reaction product of an epoxy group and a hydroxyl group.

  Regarding the polyglycidyl ether (R12) of a novolac resin that is a reaction product of various phenolic hydroxyl group-containing compounds and various aldehyde compounds, the phenolic hydroxyl group-containing compound includes, for example, phenol, naphthol, anthracenol, and the like. Examples thereof include compounds in which one or more hydrogen atoms on the aromatic nucleus are substituted with an aliphatic hydrocarbon group, an aromatic ring-containing hydrocarbon group, an alkoxy group, a halogen atom, or the like. Examples of the aldehyde compound include formaldehyde, aliphatic aldehyde compounds such as acetaldehyde and propionaldehyde; and aromatic aldehyde compounds such as benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, and hydroxynaphthaldehyde.

  Examples of the glycidyl group-containing acrylic resin (R13) include an acrylic resin having a glycidyl group-containing (meth) acrylate monomer such as glycidyl (meth) acrylate and 4-hydroxybutyl acrylate glycidyl ether as an essential component. The acrylic resin (R13) may be a homopolymer of the glycidyl group-containing (meth) acrylate monomer or may be copolymerized with other monomers. Examples of the other monomers include (meth) acrylic acid alkyl esters such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate; cyclohexyl Cyclo-ring-containing (meth) acrylates such as (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate; aromatic rings such as phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl acrylate ( (Meth) acrylates; silyl group-containing (meth) acrylates such as 3-methacryloxypropyltrimethoxysilane; styrene derivatives such as styrene, α-methylstyrene, and chlorostyrene. These may be used alone or in combination of two or more.

  These epoxy compounds may be used individually by 1 type, and may use 2 or more types together. Among them, it is preferable to use a combination of a relatively low molecular weight and a relatively high molecular weight.

  The composition (2) contains a curing agent for the epoxy compound. Examples of the curing agent include phenolic curing agents, acid curing agents, amine curing agents, amide curing agents, urea curing agents, phosphorus compounds, organic acid metal salts, Lewis acids, and amine complex salts.

  Examples of the phenolic curing agent include polyhydroxybenzene, polyhydroxynaphthalene, biphenol compound, bisphenol compound, novolac type phenol resin, phenylene or naphthylene ether type phenol resin, dicyclopentadiene-phenol addition reaction type phenol resin, and the like. Can be mentioned.

  The acid-based curing agent is tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylendoethylenetetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, methylnadic anhydride Acid anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride; malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid Aliphatic polycarboxylic acids such as fumaric acid, hexahydrophthalic acid, 1,2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, cyclopentanetetracarboxylic acid; phthalic acid, isophthalic acid, terephthalic acid, Such as pyromellitic acid and trimellitic acid Aromatic polycarboxylic acid and the like.

  Examples of the amine curing agent include aliphatic amine compounds such as ethylenediamine, tetramethylethylenediamine, triethylenetetramine, tetraethylenepentamine, 3,3′-diaminodipropylamine, butanediamine, hexanediamine, and triethanolamine; Cyclic ring-containing amine compounds such as N, N-dimethylcyclohexylamine; amine compounds having an n polyoxyalkylene structure such as polyoxyethylenediamine and polyoxypropylenediamine; piperidine, piperazine, morpholine, triethylenediamine (1,4-diazabicyclo [2 2.2] octane), pyridine, hexahydro-1,3,5-tris (3-dimethylaminopropyl) -1,3,5-triazine, 1,8-diazabicyclo- [5.4.0] -7. -Eun Heterocyclic amine compounds such as cene; phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, N-methylbenzylamine, N, N-dimethylbenzylamine, diethyltoluenediamine, xylylenediamine, α-methylbenzylmethylamine, 2, Examples include aromatic ring-containing amine compounds such as 4,6-tris (dimethylaminomethyl) phenol; imidazole compounds such as imidazole and 2-ethyl-4-methylimidazole; imidazoline compounds such as 2-methylimidazoline and the like.

  Examples of the amide-based curing agent include dicyandiamide, or a reaction product of a carboxylic acid compound such as aliphatic dicarboxylic acid or dimer acid and an amine compound.

  Examples of the urea curing agent include p-chlorophenyl-N, N-dimethylurea, 3-phenyl-1,1-dimethylurea, 3- (3,4-dichlorophenyl) -N, N-dimethylurea, N- (3-chloro-4-methylphenyl) -N ′, N′-dimethylurea and the like.

  These curing agents may be used alone or in combination of two or more. The amount of the curing agent is not particularly limited, but in the case of a curing agent that cures by reaction with the epoxy group in the epoxy compound, the ratio of the epoxy group in the epoxy compound to the functional group in the curing agent is approximately equivalent. It is preferable to blend so as to be. Moreover, in the case of the compound which acts as a curing catalyst, it is preferable to mix | blend about 0.1-20 mass% with respect to an epoxy resin.

  The said composition (2) may contain the coloring material as needed. As the coloring material, a known coloring material can be used, for example, a red coloring material such as a diketopyrrolopyrrole pigment or an anionic red organic dye; a copper halide phthalocyanine pigment, a phthalocyanine green dye, or a phthalocyanine blue color. Examples thereof include green color materials such as dyes and azo yellow organic dyes; blue color materials such as ε-type copper phthalocyanine pigments and cationic blue organic dyes.

  The composition (2) may contain various additives as necessary. Examples of additives include UV absorbers, antioxidants, photosensitizers, silicone additives, silane coupling agents, fluorine additives, rheology control agents, defoaming agents, antistatic agents, and antifogging agents. , Adhesion aids, organic fillers, inorganic fillers and the like. The addition amount of these additives is preferably in the range of 0.05 to 20% by mass in the composition (1).

  The composition (2) may contain a solvent as necessary. Solvents used are, for example, glycol ethers such as ethylene glycol monoethyl ether and diethylene glycol diethyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, ethyl acetate, propyl benzoate, carbonic acid Diethyl, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl acetoacetate, ethanol, isopropanol, phenol, diethyl ether, anisole, 2-ethoxyethanol, 1-methoxy-2-propanol, diethylene glycol, tripropylene glycol, 2-Ethoxyethyl acetate, acetone, methyl isobuty Ketones, and the like. These solvents are mainly used for adjusting the ink jet discharge property of the composition (2), and the blending amount thereof is not particularly limited.

  The composition (2) is preferably designed so that its viscosity is 1-1000 mPa · sec. The viscosity is a value measured using a rotational viscometer (manufactured by Toki Sangyo Co., Ltd .: TVE-20L). Moreover, it is preferable that the surface tension of the said composition (2) is 20-50 mN / m, and it is more preferable that it is 30-50 mN / m.

  Production of a color filter by the ink jet method using the composition (1) or (2) can be carried out by a known and conventional method. Hereinafter, an example will be described.

  The color filter includes at least a transparent substrate and a colored layer provided on the transparent substrate, and at least one of the colored layers is formed using the composition (1) or (2). Usually, the colored layer has three colored regions of R, G, and B.

  The transparent substrate may be a base material transparent to visible light, and the material thereof is not particularly limited. Specific examples include inflexible transparent rigid materials such as quartz glass, alkali-free glass, and synthetic quartz plates, and flexible transparent flexible materials such as transparent resin films and optical resin plates. It is done. The thickness of the transparent substrate is not particularly limited, but generally it is usually about 100 μm to 1 mm.

  The transparent substrate preferably has a light-shielding portion formed in a pattern like a general color filter. The light-shielding portion is a partition for adhering the composition (1) or (2) in each colored region, and is provided so as to surround each colored layer and outside the colored layer forming region. The contrast of the image can be improved.

  The light shielding part may be formed in any way, and can be formed by a known and usual method. Specific examples include metal thin films such as chromium by sputtering, vacuum deposition, etc., and resin layers containing light-shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments in resin binders. It is done. When the light-shielding part is a resin layer containing light-shielding particles, patterning is performed by development using a photosensitive resist, patterning using ink-jet ink containing light-shielding particles, and thermal transfer of the photosensitive resist. There are ways to do this. The thickness of the light shielding part is preferably about 1000 to 2000 mm in the case of a metal thin film, and preferably about 0.5 to 2.5 μm in the case of a light shielding resin layer.

  The colored layer is formed using the composition (1) or the composition (2). The arrangement of the colored layers is not particularly limited, and for example, a general arrangement such as a stripe type, a mosaic type, a triangle type, or a four-pixel arrangement type can be used. Moreover, the width | variety, area, etc. of a colored layer can be set arbitrarily. The average thickness of the colored layer is preferably in the range of 1 to 5 μm, and more preferably in the range of 1 to 2.5 μm.

  The colored layer can be formed, for example, by the following method. First, the composition (1) or the composition (2) adjusted as R, G, and B is prepared. Next, the light shielding part is patterned on the transparent substrate surface to form a colored region. Next, the ink layer is formed by selectively depositing the composition (1) or the composition (2) having a color corresponding to each of the colored layer forming regions of R, G, and B by an inkjet method. Finally, the composition (1) or the composition (2) is cured to form a colored layer.

  Regarding the curing method, when the composition used is the composition (1), it is cured by irradiation with ultraviolet rays or electron beams. In the case of curing by ultraviolet irradiation, an ultraviolet irradiation device having a xenon lamp, a high-pressure mercury lamp, a metal halide lamp, an LED lamp or the like as a light source is used, and the light amount, the arrangement of the light source, and the like are adjusted as necessary. When using a high-pressure mercury lamp, it is preferable to cure at a conveyance speed of 5 to 50 m / min for one lamp having a light quantity that is usually in the range of 80 to 160 W / cm. On the other hand, in the case of curing with an electron beam, it is preferably cured with an electron beam accelerator having an accelerating voltage that is usually in the range of 10 to 300 kV at a conveyance speed of 5 to 50 m / min. When the composition (1) contains an organic solvent, it is preferably subjected to a drying process of several seconds to several minutes under a temperature condition of about 60 to 80 ° C. before irradiating with light. Drying can be performed at a lower temperature by performing under reduced pressure conditions.

  On the other hand, when the used composition is the composition (2), it is heat-cured under a temperature condition of about 80 to 300 ° C. When the composition (2) contains an organic solvent, it is preferable to pass through a drying step of several seconds to several minutes under a temperature condition of about 60 to 150 ° C. Drying can be performed at a lower temperature by performing under reduced pressure conditions. Curing may be performed in several stages by changing the temperature condition.

  The color filter may be one in which an overcoat layer, a transparent electrode layer, an alignment film, a columnar spacer, or the like is formed in addition to the transparent substrate, the light shielding portion, and the colored layer.

  Hereinafter, the present invention will be described more specifically with reference to production examples and examples, but the present invention is not limited to these examples. Unless otherwise indicated, all parts and percentages in the examples are based on mass.

  The structural identification of the calixarene compound produced in the examples of the present application was performed mainly based on the measurement results of NMR and FD-MS under the following conditions.

¹ H-NMR was measured using “JNM-ECM400S” manufactured by JEOL RESONANCE under the following conditions.
Magnetic field strength: 400MHz
Integration count: 16 times Solvent: Deuterated chloroform Sample concentration: 2 mg / 0.5 ml

¹³ C-NMR was measured under the following conditions using “JNM-ECM400S” manufactured by JEOL RESONANCE.
Magnetic field strength: 100 MHz
Integration count: 1000 times Solvent: Deuterated chloroform Sample concentration: 2 mg / 0.5 ml

FD-MS was measured under the following conditions using “JMS-T100GC AccuTOF” manufactured by JEOL Ltd.
Measurement range: m / z = 50.00 to 2000.00
Rate of change: 25.6 mA / min
Final current value: 40 mA
Cathode voltage: -10 kV

Example 1 Production of calixarene compound (B-1) In a 300 ml four-necked flask equipped with a stirrer, a thermometer, a dropping funnel, and a reflux condenser, tert- represented by the following structural formula (a) Butyl calix [4] arene 15 g, dehydrated N, N-dimethylformamide 84.49 g, 50% NaOH aqueous solution 22.19 g were charged, heated to 65 ° C. in a nitrogen flow environment, and stirred at 300 rpm. The solution was light yellow and transparent. Next, 33.56 g of allyl bromide was added dropwise over 30 minutes using a dropping funnel. Thirty minutes after the completion of the dropwise addition, a milky white solid precipitated and became a slurry. After a further 5 hours of reaction, acetic acid and pure water were slowly added to stop the reaction. The crystals were filtered with a Kiriyama funnel, washed with methanol, and then vacuum dried to obtain 14.16 g of an allyl ether compound represented by the following structural formula (b).

In a 200 ml four-necked flask equipped with a stirrer, a thermometer, a dropping funnel, and a reflux condenser, 7 g of allyl ether compound represented by the structural formula (b), 15.95 g of dehydrated toluene, 2, 2 ′ -0.86 g of azobis (2,4-dimethylvaleronitrile) and 5.27 g of thioacetic acid were charged, heated to 65 ° C under a nitrogen flow environment, and reacted for 12 hours while stirring at 300 rpm. After cooling to room temperature, the reaction mixture was transferred to a separatory funnel, and 15 g of 1N aqueous sodium hydrogen carbonate solution and 15 g of chloroform were added to separate the organic phase. The operation of adding 15 g of chloroform to the aqueous phase to extract organic components was performed three times, and the obtained extract was combined with the organic phase recovered earlier. The organic phase was washed with a 1N aqueous sodium hydroxide solution, dehydrated by adding anhydrous magnesium sulfate to the organic phase, and filtered. The solvent was distilled off with an evaporator, and the resulting red transparent liquid was ice-cooled and methanol was added to reprecipitate crystals. The gray crystals were filtered with a Kiriyama funnel, washed with methanol, and then vacuum dried to obtain 8.754 g of a compound represented by the following structural formula (c).

  In a 100 ml four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 5 g of the compound represented by the structural formula (c), 12.94 g of tetrahydrofuran, 28.77 g of methanol, 37% concentrated hydrochloric acid 2. 669 g was charged, heated to 65 ° C. in a nitrogen flow environment, and reacted for 8 hours while stirring at 300 rpm. After cooling to room temperature, the reaction mixture was transferred to a separatory funnel, and 20 g of ion exchange water and 20 g of chloroform were added to separate the organic phase. The operation of adding 20 g of chloroform to the aqueous phase to extract organic components was performed three times, and the resulting extract was combined with the organic phase recovered earlier. The organic phase was washed with 15 g of a saturated aqueous sodium hydrogen carbonate solution and further washed with saturated brine. After anhydrous magnesium sulfate was added to the organic phase for dehydration and filtration, the solvent was distilled off with an evaporator to obtain a red transparent liquid. While cooling the red transparent liquid with ice, normal hexane and methanol were added to reprecipitate the product. The milky white crystals were filtered with a Kiriyama funnel, washed with methanol, and then vacuum dried to obtain 3.33 g of a calixarene compound (B-1) represented by the following structural formula (d).

Example 2 Production of calixarene compound (B-2) In a 100 ml four-necked flask equipped with a stirrer, a thermometer, a dropping funnel, and a reflux condenser, tert- represented by the above structural formula (a) 2 g of butylcalix [4] arene, 10 g of dehydrated N, N-dimethylformamide and 2 g of 60% sodium hydride oil dispersion were charged and reacted at room temperature for 30 minutes with stirring at 300 rpm in a nitrogen flow environment. The reaction mixture was an ocher suspension. A solution prepared by dissolving 4.585 g of bromoacetic acid in 5 g of dehydrated N, N-dimethylformamide was added dropwise over 30 minutes with a dropping funnel. 30 minutes after the completion of the dropping, an ocherous solid was deposited to form a slurry. After a further 5 hours of reaction, acetic acid and pure water were slowly added to stop the reaction. After filtering the crystals with a Kiriyama funnel and washing with methanol, 2.069 g of calixarene compound (B-2) represented by the following structural formula (e) was obtained.

Example 3 Production of calixarene compound (B-3) An allyl ether represented by the structural formula (b) above was added to a 100 ml four-necked flask equipped with a stirrer, a thermometer, a dropping funnel, and a reflux condenser. 2 g of compound, 3.55 g of dehydrated toluene, and 0.0089 g of a 5.5 mass% xylene solution of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum (0) complex were charged under a nitrogen flow environment. The mixture was reacted for 30 minutes in an ice bath with stirring at 300 rpm. Using a dropping funnel, 1.550 g of triethoxysilane was added dropwise over 30 minutes. 30 minutes after the completion of dropping, the mixture was heated to 50 ° C. and further reacted for 8 hours. The solution was light yellow and transparent. After cooling to room temperature, the platinum (0) complex was filtered with activated carbon and diatomaceous earth, and the filtrate was concentrated to obtain a pale yellow transparent liquid. The obtained liquid was vacuum-dried to obtain 2.937 g of a calixarene compound (B-3) represented by the following structural formula (f).

Example 4 Production of calixarene compound (B-4) In a 100 ml four-necked flask equipped with a stirrer, a thermometer, a dropping funnel, and a reflux condenser, tert- represented by the structural formula (a) was prepared. 1.5 g of butylcalix [4] arene, 50 g of dehydrated tetrahydrofuran, 4.8 g of 60% sodium hydride oil dispersion and 30.48 g of N- (2-bromoethyl) phthalimide were charged and stirred at 300 rpm in a nitrogen flow environment. . The reaction mixture became a pale yellow suspension. The flask was heated to reflux and allowed to react for 12 hours. After slowly adding methanol to stop the reaction, the reaction mixture was transferred to a separatory funnel, and 50 g of chloroform and 25 g of 1N hydrochloric acid were added to separate the organic phase. The operation of adding 20 g of chloroform to the aqueous phase to extract organic components was performed three times, and the resulting extract was combined with the organic phase obtained earlier. The organic phase was washed with 1M aqueous sodium hydrogen carbonate solution and further washed with ion-exchanged water, dehydrated with anhydrous magnesium sulfate, and filtered. After distilling off the solvent with an evaporator, methanol was added with ice cooling to reprecipitate the product. The milky white crystals were filtered with a Kiriyama funnel, washed with methanol, and then vacuum dried to obtain 1.503 g of a phthalimide compound represented by the following structural formula (g).

  In a 100 ml four-necked flask equipped with a stirrer, thermometer, dropping funnel, and reflux condenser, 1 g of the phthalimide compound represented by the structural formula (g), 25 g of ethanol, 95% hydrazine monohydrate 0 7940 g was charged, and the mixture was heated at 300 rpm under a nitrogen flow environment until the flask was refluxed and reacted for 5 hours. The reaction mixture became a pale yellow suspension. After cooling to room temperature, the reaction mixture was transferred to a separatory funnel, and 20 g of chloroform and 20 g of ion-exchanged water were added to separate the organic phase. The operation of adding 20 g of chloroform to the aqueous phase and extracting the organic components was repeated three times, and the resulting extract was combined with the organic phase obtained earlier. After anhydrous magnesium sulfate was added to the organic phase for dehydration and filtration, the solvent was distilled off with an evaporator. To the remaining reaction product, 10 g of methanol and 0.5908 g of 37% concentrated hydrochloric acid were added, and the mixture was heated to reflux in a nitrogen flow environment for 4 hours. The reaction mixture was cooled to room temperature, transferred to a separatory funnel, charged with 20 g of ion exchange water and 20 g of chloroform, and the organic phase was separated. The operation of adding 20 g of chloroform to the aqueous phase and extracting the organic components was repeated three times, and the resulting extract was combined with the organic phase obtained earlier. The organic phase was washed with saturated brine, dried over anhydrous magnesium sulfate, and filtered. After the solvent was distilled off with an evaporator, methanol was added to reprecipitate the product. The milky white crystals were filtered with a Kiriyama funnel, washed with methanol, and then vacuum dried to obtain 0.3978 g of a calixarene compound (B-4) represented by the following structural formula (h).

Example 5 Production of calixarene compound (B-5) In a 100 ml four-necked flask equipped with a stirrer, a thermometer, a dropping funnel, and a reflux condenser, tert- represented by the above structural formula (a) 1.5 g of butylcalix [4] arene, 50 g of dehydrated tetrahydrofuran, 1.109 g of 60% sodium hydride oil dispersion and 6.80 g of diethyl 2-bromoethylphosphonate were charged and stirred at 300 rpm in a nitrogen flow environment. The reaction mixture became a pale yellow suspension. The flask was heated to reflux and allowed to react for 12 hours. Methanol was slowly added to stop the reaction, the reaction mixture was transferred to a separatory funnel, and 50 g of chloroform and 25 g of 1N hydrochloric acid were added to separate the organic phase. The operation of adding 20 g of chloroform to the aqueous phase and extracting the organic components was repeated three times, and the resulting extract was combined with the organic phase obtained earlier. The organic phase was washed with ion-exchanged water, dehydrated by adding anhydrous magnesium sulfate, and filtered. After distilling off the solvent with an evaporator, methanol was added with ice cooling to reprecipitate the product. The milky white crystals were filtered with a Kiriyama funnel, washed with methanol, and then vacuum dried to obtain 1.85 g of a phosphonic acid ester compound represented by the following structural formula (i).

  In a 100 ml four-necked flask equipped with a stirrer, thermometer, dropping funnel, and reflux condenser, 1.266 g of the phosphonate compound represented by the structural formula (i), 10 g of dehydrated acetonitrile, trimethylsilyl bromide 2.449 g was charged, heated under reflux in a nitrogen flow environment at 300 rpm until the inside of the flask was refluxed, and reacted for 6 hours. The reaction mixture became a pale yellow suspension. 5 g of methanol was added and heated until the inside of the flask was refluxed, and reacted for 12 hours. Further, 5 g of methanol was added and reacted for 2 hours. After cooling to room temperature, the reaction mixture was transferred to a separatory funnel, and 20 g of chloroform and 20 g of ion-exchanged water were added to separate the organic phase. The operation of adding 10 g of chloroform to the aqueous phase to extract the organic component mainly was repeated three times, and the resulting extract was combined with the organic phase obtained earlier. The organic phase was dehydrated by adding anhydrous magnesium sulfate and filtered. After distilling off the solvent with an evaporator, methanol was added with ice cooling to reprecipitate the product. The milky white crystals were filtered with a Kiriyama funnel, washed with methanol, and then vacuum dried to obtain 0.758 g of calixarene compound (B-5) represented by the following structural formula (j).

Example 6 Production of calixarene compound (B-6) In a 1 liter four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, tert-butylcalix represented by the structural formula (a) [4 ] 50 g of arene, 32.26 g of phenol and 350 ml of dehydrated toluene were charged and stirred at 300 rpm in a nitrogen flow environment. The tert-butylcalix [4] arene was suspended without dissolving. While the flask was immersed in an ice bath, 51.37 g of anhydrous aluminum chloride (III) was added in several portions. The color of the solution changed to light orange and transparent, and anhydrous aluminum (III) chloride was precipitated at the bottom. After stirring at room temperature for 5 hours, the reaction mixture was transferred to a 1 L beaker, and the reaction was stopped by adding ice, 100 ml of 1N hydrochloric acid, and 350 ml of toluene. The color of the solution changed to light yellow and transparent. The reaction mixture was transferred to a separatory funnel and the organic phase was recovered. The operation of adding 100 ml of toluene to the aqueous phase to extract organic components was performed three times, and the resulting extract was combined with the organic phase recovered earlier. After anhydrous magnesium sulfate was added to the organic phase for dehydration, the organic phase was recovered by filtration. The solvent was distilled off with an evaporator to obtain a mixture of white crystals and a colorless transparent liquid. While stirring the mixture, methanol was slowly added to reprecipitate the product that had been dissolved in the liquid. The white crystals were filtered with a Kiriyama funnel, washed with methanol, and then vacuum dried to obtain 29.21 g of a compound represented by the following structural formula (k).

  10.200 g of butyryl chloride and 101.5 g of nitrobenzene were stirred in a 200 ml four-necked flask equipped with a stirrer, a thermometer and a reflux condenser. While the flask was immersed in an ice bath, 16.96 g of anhydrous aluminum (III) chloride was added in several portions. The color of the solution changed to light orange and transparent, and anhydrous aluminum (III) chloride was precipitated at the bottom. After stirring for 30 minutes at room temperature, 7 g of the compound represented by the structural formula (k) was added in several portions. The reaction mixture foamed to become an orange transparent solution. After that, the contents were transferred to a 1 L beaker, and the reaction was stopped by slowly adding ice, 100 ml of 1N hydrochloric acid and 30 g of chloroform, and the color of the solution became light yellow and transparent, and the reaction mixture was transferred to a separatory funnel. The organic phase was recovered, the process of adding 30 g of chloroform to the aqueous phase and extracting the organic components was repeated three times, and the resulting extract was combined with the previously obtained organic phase. After dehydration and filtration, the solvent was distilled off with an evaporator to obtain a yellow transparent liquid.Methanol was added to the obtained yellow transparent liquid while cooling with ice to reprecipitate the product. After filtering the white crystals Recrystallization from chloroform and methanol to give an additional compound 8.018g that was vacuum dried represented by the following structural formula (l).

  In a 300 ml four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 7 g of the compound represented by the structural formula (l) and 81.44 g of diethylene glycol monoethyl ether were added and stirred. After adding 2.585 g of hydrazine monohydrate, 6.809 g of potassium hydroxide pellets were added. After heating to 100 ° C. and stirring for 30 minutes, the flask was heated to reflux and allowed to react for 12 hours. After cooling to 90 ° C., 30 g of ion exchange water was added and stirred for 30 minutes. After cooling to room temperature, the mixed solution was transferred to a beaker, and 100 ml of 1N hydrochloric acid and 30 g of chloroform were added. The mixture was transferred to a separatory funnel and the organic phase was separated. The operation of adding 30 g of chloroform to the aqueous phase and extracting the organic component was repeated three times, and the resulting extract was combined with the organic phase obtained earlier. The organic phase was dehydrated by adding anhydrous magnesium sulfate and filtered. The solvent was distilled off with an evaporator to obtain an orange viscous liquid, and hexane and methanol were added to reprecipitate the product. The white crystals were filtered with a Kiriyama funnel, and the resulting milky white crystals were vacuum dried to obtain 4.156 g of a compound represented by the following structural formula (m).

  In Example 1, instead of the tert-butylcalix [4] arene represented by the structural formula (a), the compound represented by the structural formula (m) was used and reacted in the same manner as in Example 1, An allyl etherified product represented by the following structural formula (n) was obtained. Furthermore, instead of the allyl ether compound represented by the structural formula (b), an allyl ether compound represented by the following structural formula (n) was used and reacted in the same manner as in Example 1 to obtain the following structural formula (o). The calixarene compound (B-6) represented by these was obtained.

Example 7 Production of calixarene compound (B-7) In Example 2, the compound represented by the structural formula (m) instead of the tert-butylcalix [4] arene represented by the structural formula (a) Was used in the same manner as in Example 2 to obtain a calixarene compound (B-7) represented by the following structural formula (p).

Example 8 Production of calixarene compound (B-8) In Example 3, an allyl etherified compound represented by the structural formula (n) was used instead of the allyl etherified compound represented by the structural formula (b). Reaction was carried out in the same manner as in Example 3 to obtain a calixarene compound (B-8) represented by the following structural formula (q).

Example 9 Production of calixarene compound (B-9) In Example 4, the compound represented by the structural formula (m) instead of the tert-butylcalix [4] arene represented by the structural formula (a) Was used in the same manner as in Example 4 to obtain a calixarene compound (B-9) represented by the following structural formula (r).

Example 10 Production of calixarene compound (B-10) In Example 5, the compound represented by the structural formula (m) instead of the tert-butylcalix [4] arene represented by the structural formula (a) Was used in the same manner as in Example 5 to obtain a calixarene compound (B-10) represented by the following structural formula (s).

Examples 1 to 10 Production and Evaluation of Surface-Modified Semiconductor Nanocrystals Surface-modified semiconductor nanocrystals were produced in the following manner, and various evaluation tests were performed. The results are shown in Table 1.
<Manufacture of surface-modified semiconductor nanocrystals>
A 100 ml flask was charged with 2.33 g of indium acetate, 4.0 g of trioctylphosphine oxide, and 4.8 g of lauric acid, and stirred at 160 ° C. for 40 minutes while bubbling with nitrogen gas. The mixture was further stirred at 250 ° C. for 20 minutes, and then heated to 270 ° C. and stirring was continued. Tris (trimethylsilyl) phosphine was dissolved in trioctylphosphine in the glove box to prepare a 25% by mass solution, and 6.0 ml was filled in a glass syringe. This was poured into a flask maintained at 270 ° C. and reacted at 250 ° C. for 5 minutes. The flask was cooled to room temperature, and 10 ml of toluene and 40 ml of ethanol were added to aggregate the fine particles. After the fine particles were precipitated using a centrifuge, the supernatant was discarded, and the precipitated fine particles were dissolved in trioctylphosphine. This operation was repeated three times to wash the unreacted raw material, thereby obtaining a trioctylphosphine solution of indium phosphide (InP) fine particles.

  The trioctylphosphine solution of indium phosphide (InP) fine particles obtained above was put into a 100 ml flask so that the amount of fine particles of indium phosphide (InP) was 120 mg. 2.53 g of zinc stearate was dissolved in 15 ml of trioctylphosphine, and 0.1 g of calixarene compound was further added and dissolved to obtain a solution (1). A solution (2) was prepared by dissolving 0.3 g of thioacetamide in 15 ml of trioctylphosphine. The solution (1) and the solution (2) were mixed to obtain a zinc sulfide (ZnS) solution. A quarter of zinc sulfide (ZnS) solution was put into the flask, heated to 200 ° C. and stirred for 30 minutes, and then cooled to 80 ° C. This operation was repeated four times to charge the entire amount of zinc sulfide (ZnS) solution. After completion of the reaction, the flask was cooled to room temperature, and 30 ml of toluene and 200 ml of ethanol were added to aggregate the fine particles. The target surface-modified semiconductor nanocrystal was obtained as a precipitate using a centrifuge.

<Dispersion stability test>
The obtained surface-modified semiconductor nanocrystals were dissolved in toluene, propylene glycol monomethyl ether acetate, and ethyl acetate, and evaluated by the presence or absence of turbidity or precipitation.
A: There is no precipitate in the solvent and there is no turbidity.
B: Precipitate exists in the solvent or the solution is cloudy.

<Measurement of weight loss during heating>
The surface-modified semiconductor nanocrystals were completely dried up with a vacuum dryer, and about 5 mg was weighed on an aluminum pan. The weight loss when the temperature was raised to 600 ° C. at a temperature rising rate of 10 ° C. per minute was measured with a TG-DTA apparatus (EXSTAR TG / DTA 6200) manufactured by SII and evaluated according to the following criteria. The smaller the weight loss, the higher the semiconductor nanocrystal concentration.
A: Weight reduction amount less than 15 wt% B: Weight reduction amount 15 wt% or more

Comparative Examples 1 and 2 Production and evaluation of surface-modified semiconductor nanocrystals for comparison In Example 1, the same comparison was performed except that 0.1 g or 4 g of trioctylphosphine oxide (TOPO) was used instead of the calixarene compound. Surface-modified semiconductor nanocrystals for use were obtained. About the obtained surface modification semiconductor nanocrystal for a comparison, various evaluation tests were done like the Example. The results are shown in Table 1.

Comparative Example 3 Production and Evaluation of Surface-Modified Semiconductor Nanocrystals for Comparison A fine particle was aggregated by adding 200 ml of ethanol to 30 ml of a toluene dispersion of InP / ZnS quantum dots (manufactured by Optosilius). Using a centrifuge, a surface-modified semiconductor nanocrystal for comparison was obtained as a precipitate. About the obtained surface modification semiconductor nanocrystal for a comparison, various evaluation tests were done like the Example. The results are shown in Table 1.

Claims (6)

Semiconductor nanocrystal (A) and the following structural formula (1)

(Wherein R ¹ is an aliphatic hydrocarbon group which may have any of an ether bond site, a carbonyl group and a hydroxyl group. R ² is a polar group or a structural site having a polar group. R ³ Is a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, or an aryl group which may have a substituent, n is an integer of 2 to 10. * is an aromatic ring Is the point of attachment to.)
A surface-modified semiconductor nanocrystal having a calixarene compound (B) having a molecular structure represented by the formula: The calixarene compound (B) is
The following structural formula (1-1) or (1-2)

(Wherein R ¹ is an aliphatic hydrocarbon group which may have any of an ether bond site, a carbonyl group and a hydroxyl group. R ² is a polar group or a structural site having a polar group. R ³ Is a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, or an aryl group which may have a substituent, where n is an integer of 2 to 10.)
The surface modified semiconductor nanocrystal of Claim 1 which has the molecular structure represented by these. The polar group in which R ² is any one of a hydroxyl group, an amino group, a carboxy group, a thiol group, a phosphoric acid group, a phosphonic acid group, a phosphinic acid group, a phosphine oxide group, and an alkoxysilyl group, or a structure having these polar groups The surface-modified semiconductor nanocrystal according to claim 1, which is a site. The resin composition containing the to-be-surface-modified semiconductor nanocrystal as described in any one of Claims 1-3. The color filter which uses the to-be-surface-modified semiconductor nanocrystal as described in any one of Claims 1-3. A display comprising the color filter according to claim 5.